The invention relates to new substituted 1-arylpyrazoles, to a plurality of processes for their preparation, and to their use as pesticides.
It has already been disclosed that certain substituted 1-arylpyrazoles, such as, for example, 5-amino-1-[2,6-dichloro-4-(trifluoromethyl)-phenyl]-3-cyano-4-[(trifluoromethyl)-sulphinyl]-1H-pyrazole, have a good activity against pests (cf. for example EP-A 295 117 and EP-A 352 944).
Moreover, a large number of substituted 1-arylpyrazoles are described which can be employed for combating pests (cf. for example EP-A 201 852, EP-A 418 016).
In addition, substituted 1-arylpyrazoles are also used as intermediates for the preparation of pesticides (cf. for example EP-A 301 338, EP-A 301 339, EP-A 374 061, EP-A 260 521).
However, the level and duration of action of the previously known compounds is not entirely satisfactory in all fields of application, in particular in the case of certain insects or when low application concentrations are used.
New substituted 1-arylpyrazoles of the general formula (I) 
in which
R1 represents hydrogen, cyano, alkyl, alkoxyalkyl, alkylthioalkyl, halogenoalkyl or cyanoalkyl,
R2 represents difluoroethyl or trifluoroethyl,
R3 represents hydrogen, amino, halogen or one of the following groups 
in which
R4 represents alkyl, halogenoalkyl, alkoxyalkyl or optionally substituted phenyl,
R5 represents hydrogen or alkyl,
R6 represents hydrogen, alkyl or optionally substituted phenyl and
R7 represents alkyl or
R5 and R6 together with the carbon atom to which they are bonded represent an optionally substituted heterocycle,
Ar represents optionally substituted phenyl or pyridyl and
n represents a number 0, 1 or 2,
have now been found.
Furthermore, it has been found that the new substituted 1-arylpyrazoles of the general formula (I) are obtained by one of the processes described below:
a) Substituted 1-aryl-4-mercapto-pyrazoles of the formula (Ia) 
in which
R1, R2, Ar and n have the abovementioned meaning and R3-1 represents hydrogen or amino, are obtained when pyrazole derivatives of the formula (II) 
in which
R1, R3-1 and Ar have the abovementioned meanings, are reacted with sulphenyl halides of the formula (III)
R2xe2x80x94Sxe2x80x94Hal xe2x80x83xe2x80x83(III) 
in which
R2 has the abovementioned meaning and Hal represents halogen, in particular chlorine or bromine,
if appropriate in the presence of a diluent and if appropriate in the presence of a reaction auxiliary.
b) Substituted 1-arylpyrazoles of the formula (Ib) 
in which
R1, R2, R3-1 have the abovementioned meanings and
n represents the number 1 or 2,
are obtained when compounds of the formula (Ia) 
in which
R1, R2 and R3-1 have the abovementioned meanings,
are oxidized using oxidants, if appropriate in the presence of a diluent and if appropriate in the presence of a catalyst.
Other preparation methods for the compounds of the formula (I) according to the invention are given hereinbelow by way of example, but not by limitation, R1, R2, R4, R5, R6, R7, Ar and n having the abovementioned meaning:
c) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with acid halides of the formula (IV) (Hal=chlorine): 
d) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with acetals of the formula (V) (R8=alkyl): 
e) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with tetrahydrofuran derivatives of the formula (VI) (R8=alkyl): 
f) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with aldehydes or ketones of the formula (VII): 
g) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with ortho esters of the formula (VIII): 
h) Reaction of substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with tribromomethane, of the formula (IX): 
i) Reaction of Substituted 1-arylpyrazoles of the formula (Ic) (R3-1=NH2) with nucleophiles NU: 
The invention preferably relates to compounds of the formula (I) in which
R1 represents hydrogen, cyano, (C1-C6)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, (C1-C4) -halogenoalkyl or (C1-C2)-cyanoalkyl,
R2 represents difluoroethyl or trifluoroethyl,
R3 represents hydrogen, amino, halogen or one of the following groups 
in which
R4 represents (C1-C6)-alkyl, (C1-C6)-halogenoalkyl having 1-3 halogen atoms, (C1-C6)-alkoxy-(C1-C6)-alkyl, or phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents,
R5 represents hydrogen or (C1-C6)-alkyl,
R6 represents hydrogen, (C1-C6)-alkyl, or phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents,
R7 represents (C1-C6)-alkyl or
R5 and R6 together with the carbon atom to which they are bonded represent optionally substituted pyridyl,
Ar represents phenyl or pyridyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents from the series comprising halogen, halogeno (C1-C6)alkyl, halogeno(C1-C6)alkylthio, halogeno(C1-C6)alkoxy, alkoxy, hydrazino, (C1-C6)-dialkylhydrazino, amino, amino(C1-C6)alkyl, diamino(C1-C6)alkyl, imino(C1-C6)-alkyl, cyano, (C1-C6)alkylthio or the group 
in which
R9 and R10 are identical or different and represent hydrogen or (C1-C6)-alkyl, and
n represents a number 0, 1 or 2.
In particular, the invention relates to compounds of the formula (I) in which
R1 represents hydrogen, cyano, (C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C2)-alkyl, (C1-C2)-halogenoalkyl having 1 to 5 identical or different fluorine, chlorine or bromine atoms, or cyanomethyl,
R2 represents difluoroethyl or trifluoroethyl,
R3 represents hydrogen, amino, bromine or one of the following groups 
in which
R4 represents (C1-C4)-alkyl, (C1-C4)-halogenoalkyl having 1-3 halogen atoms, (C1-C4) -alkoxy-(C1-C2)-alkyl, or phenyl which is optionally monosubstituted to trisubstituted by identical or different substituents,
R5 represents hydrogen or (C1-C4)-alkyl,
R6 represents hydrogen, (C1-C4)-alkyl, phenyl which is optionally monosubstituted or disubstituted by identical or different substituents, or 4-hydroxy-3-methoxy-phenyl,
R7 represents (C1-C4)-alkyl or
R5 and R6 together with the carbon atom to which they are bonded represent optionally substituted pyridyl,
Ar represents phenyl or pyridyl, each of which is optionally monosubstituted to trisubstituted by identical or different substituents from the series comprising fluorine, chlorine, trifluoromethyl, trifluoromethylthio, trifluoromethoxy, methoxy, hydrazino, dimethylhydrazino, amino, methylamino, dimethylamino, iminomethyl, cyano, methylthio or the group 
in which
R9 and R10 are identical or different and represent hydrogen or (C1-C4)-alkyl, and
n represents a number 0, 1 or 2.
Very particularly preferred compounds of the formula (I) are those in which
R1 represents hydrogen, cyano, (C1-C4)-alkyl, methoxymethyl, ethoxymethyl, methoxyethyl, ethoxyethyl, trifluoromethyl, bromomethyl or cyanomethyl,
R2 represents 1,1-difluoroethyl or 2,2,2-trifluoroethyl,
Ar represents phenyl which is disubstituted or trisubstituted by identical or different substituents, substituents in the 2-position being fluorine or chlorine, in the 4-position trifluoromethyl and in the 6-position fluorine, chlorine, cyano, methoxy, methylthio, trifluoromethyl, trifluoromethoxy or trifluoromethylthio, or
Ar represents a 2-pyridyl radical which is substituted in the 4-position by trifluoromethyl and in the 6-position by fluorine or chlorine, and
R3 and n have the abovementioned meanings.
The abovementioned general definitions or those where preferred ranges have been mentioned apply to the end products of the formula (I) and, analogously, to the starting materials or intermediates required in each case for the preparation. The definitions can be combined with each other, that is to say any desired combinations between the preferred ranges indicated are possible.
The hydrocarbon radicals mentioned in the definition of the radicals, such as alkyl, alkoxy, alkoxyalkyl and alkylthio, are straight-chain or branched, even if this is not stated expressly.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, in particular fluorine or chlorine.
The following substituted 1-arylpyrazoles of the general formula (I) may be mentioned individually in addition to the compounds mentioned in the Preparation Examples:
If, for example, 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-methyl-pyrazole and 1,1-difluoroethylsulphenyl chloride are used as starting substances, the course of the reaction of process (a) according to the invention can be represented by the following equation: 
If, for example, 5-amino-3-methoxymethyl-4-(2,2,2-trifluoromethylthio)-1-[(3-chloro-5-trifluoromethyl)-2-pyridyl]-pyrazole is used as starting substance, H2O2 as oxidant and sodium tungstate as catalyst, the course of the reaction of process (b) according to the invention can be represented by the following equation: 
If, for example, 5-amino-4-(1,1-difluoroethylthio)-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-3-methoxymethylpyrazole and methoxyacetyl chloride are used as starting substances, the course of the reaction of process (c) according to the invention can be represented by the following equation: 
If, for example, 5-amino-3-cyano-4-(1,1-difluoroethylthio)-1-thio)-1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazole and dimethylformamide dimethyl acetal are used as starting substances, the course of the reaction of process (d) according to the invention can be represented by the following equation: 
If, for example, 5-amino-4-(1,1-difluoroethylthio) -1-(2,6-dichloro-4-trifluoromethyl-phenyl)-pyrazole and 2,5-dimethoxytetrahydrofuran are used as starting substances, the course of the reaction of process (e) according to the invention can be represented by the following equation: 
If, for example, 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-methyl-4-(1,1-difluoroethylthio)-pyrazole and 3-methoxy-4-hydroxybenzaldehyde are used as starting substances, the course of the reaction of process (f) according to the invention can be represented by the following equation: 
If, for example, 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-methyl-4-(1,1-difluoroethylthio)-pyrazole and ethyl orthoformate are used as starting substances, the course of the reaction of process (g) according to the invention can be represented by the following equation: 
If, for example, 5-amino-4-(1,1-difluoroethylthio)-1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazole, tribromomethane and tert-butyl nitrite are used as starting substances, the course of the reaction of process (h) according to the invention can be represented by the following equation: 
If, for example, 5-amino-4-(1,1-difluoroethylthio)-1-(2,6-dichloro-4-trifluoromethylphenyl)-pyrazole and hydrazine hydrate are used as starting substances, the course of the reaction of process (i) according to the invention can be represented by the following equation: 
Some of the pyrazole derivatives of the formula (II) to be used as starting substances for carrying out process (a) according to the invention are known, or they can be obtained by known processes (cf. for example EP-A 295 117, EP-A 154 115, EP-A 201 852).
The pyrazole derivatives of the formula (IIa) 
in which
R3-1 and Ar have the abovementioned meaning, are new and a subject of the invention.
The compounds of the formula (IIa) can be obtained by generally customary and known processes by heating bromomethyl-pyrazoles of the formula (IIb) 
in which
R3-1 and Ar have the abovementioned meaning, together with alkali metal cyanides, such as, for example, sodium cyanide or potassium cyanide, if appropriate in the presence of an inert diluent, such as, for example, water, and in the presence of a phase transfer catalyst, such as, for example, TEBA, at temperatures between 40xc2x0 C. and 100xc2x0 C., preferably 70xc2x0 C. to 100xc2x0 C. (cf. Preparation Example).
If, for example, 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-bromomethyl-pyrazole is used as starting substance and an aqueous sodium cyanide solution and TEBA as phase transfer catalyst, the course of the reaction of the process according to the invention can be represented by the following equation: 
The bromomethylpyrazoles of the formula (IIb), which are required as starting compounds for the preparation of the pyrazole derivatives of the formula (IIa), are new and a subject of the invention.
Compounds of the formula (IIb) are obtained by generally customary and known processes by heating methoxymethylpyrazoles of the formula (IIc): 
in which
R3-1 and Ar have the abovementioned meaning, together with a 48% strength solution of hydrogen bromide in glacial acetic acid at temperatures between 60xc2x0 C. and 130xc2x0 C., preferably at temperatures between 90xc2x0 C. and 130xc2x0 C. (cf. Preparation Examples).
If, for example, 5-amino-1-(2,6-dichloro-4-trifluoromethylphenyl)-3-methoxypyrazole and 48% strength solution of hydrogen bromide in glacial acetic acid are used as starting substances, the course of the reaction of the process according to the invention can be represented by the following equation: 
The methoxymethylpyrazoles of the formula (IIc), which are required as starting compounds for the preparation of the bromomethylpyrazole derivatives of the formula (IIb), are new and also a subject of the invention.
The compounds of the formula (IIc) can be obtained by heating arylhydrazines of the formula (X)
Arxe2x80x94NHNH2 xe2x80x83xe2x80x83(X) 
in which
Ar has the abovementioned meaning, together with 2-amino-1-cyano-3-methoxy-propene of the formula (XI) 
if appropriate in the presence of an inert organic solvent, such as, for example, alcohols, preferably methanol or ethanol, or acetic acid, or mixtures of methanol and acetic acid or ethanol and acetic acid, at temperatures between 50xc2x0 C. and 130xc2x0 C., preferably 60xc2x0 C. and 120xc2x0 C. To carry out the process, 1 to 4 mol, preferably 1 to 2 mol, of 1-cyano-2-amino-3-methoxy-propene of the formula (XI) is generally employed per mole of arylhydrazine of the formula (X) . The reaction is carried out and the compounds of the formula (IVc) are worked up and isolated in the customary manner.
If, for example, 2,6-dichloro-4-trifluoromethylphenylhydrazine and 1-cyano-2-amino-3-methoxy-propene are used as starting substances, the course of the reaction of the process according to the invention can be represented by the following equation: 
The arylhydrazines of the formula (X) , which are required as starting substances, are generally known compounds of organic chemistry.
2-Amino-1-cyano-3-methoxypropene, of the formula (XI), which is furthermore required for the preparation of the methoxymethylpyrazoles of the formula (IIc), is new and a subject of the invention.
2-Amino-1-cyano-3-methoxy-propene, of the formula (XI), is obtained when methoxyacetonitrile, of the formula (XII),
CH3OCH2xe2x80x94CN xe2x80x83xe2x80x83(XII) 
is heated together with acetonitrile and, if appropriate, in the presence of an inert organic solvent, such as, for example, ethers, preferably diethyl ether, dibutyl ether, glycol dimethyl ether and diglycol methyl ether, tetrahydrofuran and dioxane, or in mixtures of acetonitrile and these solvents and in the presence of bases, such as, for example, sodium hydride or potassium tert-butylate, at temperatures between 20xc2x0 C. and 150xc2x0 C., preferably 20xc2x0 C. and 100 xc2x0 C. To carry out the process, methoxyacetonitrile, the base in question and acetonitrile are generally employed in approximately-equimolar amounts. However, it is also possible to use one of the two components employed in each case in a larger excess. The reaction is carried out and the compounds of the formula (XI) are worked up and isolated in the customary manner (cf. Preparation Examples).
The compound of the formula (XI) can exist in the form of geometric isomers (E/Z isomers) or of variously composed mixtures of isomers. The invention claims the use of the pure isomers as well as of the isomer mixtures. For simplicity""s sake, the text hereinbelow will always mention compounds of the formula (XI), even though this is to be understood as meaning the pure compounds and also their mixtures which contain various amounts of E/Z isomers.
Formula (III) provides a general definition of the sulphenyl halides furthermore required as starting substances for carrying out the process (a) according to the invention. In this formula (III), R2 preferably represents those radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for this substituent.
The sulphenyl halides of the formula (III) are generally known compounds of organic chemistry.
Formula (Ia) provides a general definition of the 1-aryl-4-mercapto-pyrazoles required as starting substances for carrying out the process (b) according to the invention. In this formula (Ia), R1, R2, R3-1 and Ar preferably represent those radicals and indices which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (Ia) are compounds according to the invention and can be obtained by process (a).
Formula (Ic) provides a general definition of the 1-aryl-4-pyrazoles required as Starting substances for carrying out the processes (c), (d), (e), (f), (g), (h) and (i) according to the invention. In this formula (Ic), R1, R2, Ar and n preferably represent those radicals and indices which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention as being preferred for these substituents.
The compounds of the formula (Ic) are compounds according to the invention and can be obtained by processes (a) or (b).
The compounds of the formulae (IV), (V), (VI), (VII), (VIII) and (IX), which are furthermore required as starting compounds, are generally known compounds of organic chemistry.
Suitable nucleophiles (NuI) for carrying out the process (i) according to the invention are all customary reagents of organic chemistry which are suitable for such reactions. Examples which may be mentioned, but not by limitation, are: alcoholates, hydrazine derivatives and cyanides.
Suitable diluents for carrying out the process (a) according to the invention are inert organic solvents. These include, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform and carbon tetrachloride; ethers, such as diethyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether, ketones, such as acetone or butanone, nitriles, such as acetonitrile or propionitrile; amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide, esters, such as ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or acids, such as, for example, acetic acid.
If appropriate, process (a) according to the invention can be carried out in the presence of a reaction auxiliary. Suitable reaction auxiliaries are all customary inorganic or organic bases. These include, for example, alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate or sodium hydrogen carbonate, and also tertiary amines, such as triethylamine, N,N-dimethylaniline, pyridine, N,N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU).
When carrying out the process (a) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between xe2x88x9220xc2x0 C. and +120xc2x0 C., preferably at temperatures between 0xc2x0 C. and +50xc2x0 C.
For carrying out the process (a) according to the invention, 1.0 to 2.5 mol, preferably 1.0 to 1.5 mol, of sulphenyl halide of the formula (III) and, if appropriate, 1.0 to 2.5 mol, preferably 1.0 to 1.5 mol, of reaction auxiliary are generally employed per mole of pyrazole derivatives of the formula (II). The reaction is carried out and the reaction products of the formula (Ia) are worked up and isolated by generally customary processes.
Suitable oxidants for carrying out the process (b) according to the invention are all customary oxidants which can be used for the oxidation of sulphur. Particularly suitable are hydrogen peroxide, organic peracids, such as, for example, peracetic acid, m-chloroperbenzoic acid, p-nitroperbenzoic acid or atmospheric oxygen.
Diluents which are suitable for carrying out the process (b) according to the invention are also inert organic solvents. The following are preferably used: hydrocarbons, such as benzine, benzene, toluene, hexane or petroleum ether; chlorinated hydrocarbons, such as dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride or chlorobenzene; ethers, such as diethyl ether, dioxane or tetrahydrofuran; carboxylic acids, such as acetic acid or propionic acid, or dipolar aprotic solvents, such as acetonitrile, acetone, ethyl acetate or dimethylformamide.
If appropriate, process (b) according to the invention can be carried out in the presence of an acid-binding agent. All organic and inorganic acid-binding agents which can conventionally be used are suitable. The following are preferably used: alkaline earth metal hydroxides, alkaline earth metal acetates, alkaline earth metal carbonates, alkali metal hydroxides, alkali metal acetates or alkali metal carbonates, such as, for example, calcium hydroxide, sodium hydroxide, sodium acetate or sodium carbonate.
If appropriate, process (b) according to the invention can be carried out in the presence of a suitable catalyst. All metal salt catalysts which are generally customary for such sulphur oxidations are suitable. Ammonium molybdate and sodium tungstate may be mentioned in this context by way of example.
When carrying out the process (b) according to the invention, the reaction temperatures can be varied within a substantial range. In general, the process is carried out at temperatures between xe2x88x9220xc2x0 C. and +70xc2x0 C., preferably at temperatures between 0xc2x0 C. and +50xc2x0 C.
To carry out process (b) according to the invention, 0.8 to 1.2 mol, preferably equimolar amounts, of oxidant are generally employed per mole of substituted 1-arylpyrazole of the formula (Ia), if it is intended to interrupt the oxidation of the sulphur at the sulphoxide level. 1.8 to 3.0 mol, preferably twice the molar amounts, of oxidant are generally employed per mole of substituted 1-arylpyrazole of the formula (Ia) to oxidize the sulphoxide to the sulphone. The reaction is carried out and the end products of the formula (Ib) are worked up and isolated by customary processes.
The active compounds are well tolerated by plants, have a favourable toxicity to warm-blooded species and are suitable for combating animal pests, in particular insects, arachnids and nematodes, which occur in agriculture, in forests, in the protection of stored products and of materials, and in the hygiene sector. They can preferably be used as plant protection agents. They are active .against normally sensitive and resistant species and against all or individual development stages. They abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgate and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanura, for example, Lepisma saccharina.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanlea, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anopolura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp., Bovicola spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piestoa quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Photodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, naodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Psuedococcus spp. and Psylla spp.
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp., Ctenocephalides spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
From the order of the Acarina, for example, Acarus siro, Argas. spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amhlyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.
The plant-parasitic nematodes include Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. and Trichodorus spp.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances and in coating compositions for seed, and furthermore in formulations used with burning equipment, such as fumigating cartridges, fumigating cans, fumigating coils and the like, as well as ULV cold mist and warm mist formulations.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water; by liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenohydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-disperse silica, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
The active compounds according to the invention can be present in their commercially available formulations and in the use forms, prepared from the formulations, as a mixture with other active compounds, such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungitides, growth-regulating substances or herbicides. The insecticides include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas and substances produced by microorganisms.
The following compounds may be mentioned:
acrinathrin, alphamethrin, betacyfluthrin, bifenthrin, brofenprox, cis-resmethrin, clocythrin, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, fluvalinate, lambda-cyhalothrin, permethrin, pyresmethrin, pyrethrum, silafluofen, tralomethrin, zetamethrin,
alanycarb, bendiocarb, benfuracarb, bufencarb, butocarboxim, carbaryl, cartap, ethiofencarb, fenobucarb, fenoxycarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, promecarb, propoxur, terbam, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb,
acephate, azinphos A, azinphos M, bromophos A, cadusafos, carbophenothion, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos M, cyanophos, demeton M, demeton-S-methyl, demeton S, diazinon, dichlorvos, dicliphos, dichlorfenthion, dicrotophos, dimethoate, dimethylvinphos, dioxathion, disulfoton, edifenphos, ethion, etrimphos, fenitrothion, fenthion, fonophos, formothion, heptenophos, iprobenfos, isazophos, isoxathion, phorate, malathion, mecarbam, mevinphos, mesulfenphos, methacrifos, methamidophos, naled, omethoate, oxydemeton M, oxydeprofos, parathion A, parathion M, phenthoate, phorate, phosalone, phosmet, phosphamdon, phoxim, pirimiphos A, pirimiphos M, propaphos, prothiophos, prothoate, pyraclophos, pyridaphenthion, quinalphos, salithion, sebufos, sulfotep, sulprofos, tetrachlorvinphos, temephos, thiomethon, thionazine, trichlorfon, triazophos, vamidothion,
buprofezin, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, pyriproxifen, tebufenozide, teflubenzuron, triflumuron,
imidacloprid, nitenpyram, N-[(6-chloro-3-pyridinyl)methyl]-Nxe2x80x2-cyano-N-methylethane-imide-amide (NI-25),
abamectin, amitrazine, avermectin, azadirachtin, bensultap, Bacillus thuringiensis, cyromazine, diafenthiuron, emamectin, ethofenprox, fenpyrad, fipronil, flufenprox, lufenuron, metaldehyde, milbemectin, pymetrozine, tebufenpyrad, triazuron,
aldicarb, bendiocarb, benfuracarb, carbofuran, carbosulfan, chlorethoxyfos, cloethocarb, disulfoton, ethophrophos, etrimphos, fenamiphos, fipronil, fonofos, fosthiazate, furathiocarb, HCH, isazophos, isofenphos, methiocarb, monocrotophos, nitenpyram, oxamyl, phorate, phoxim, prothiofos, pyrachlofos, sebufos, silafluofen, tebupirimiphos, tefluthrin, terbufos, thiodicarb, thiafenox,
azocyclotin, butylpyridaben, clofentezine, cyhexatin, diafenthiuron, diethion, emaanectin, fenazaquin, fenbutatin oxide, fenothiocarb, fenpropathrin, fenypyrad, fenpyroximate, fluazinam, fluazuron, flucycloxuron, flufenoxuron, fluvalinate, fubfenprox, hexythiazox, ivemectin, methidathion, monocrotophos, moxidectin, naled, phosalone, profenofos, pyraclofos, pyridaben, pyrimidifen, tebufenpyrad, thuringiensin, triarathene and 4-bromo -2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile (AC 303630).
The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.
The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 1% by weight.
The compounds are employed in a customary manner appropriate for the use forms.
When used against hygiene pests and pests of stored products, the active compounds are distinguished by an excellent-residual action on wood and clay as well as a good stability to alkali.
The preparation of the compounds of the formula (I) according to the invention will be illustrated with the aid of the following Examples:
Unless otherwise indicated, percentages are by weight.